Chemical solution deposition method of fabricating highly aligned MgO templates

ABSTRACT

A superconducting article includes a substrate having an untextured metal surface; an untextured barrier layer of La 2 Zr 2 O 7  or Gd 2 Zr 2 O 7  supported by and in contact with the surface of the substrate; a biaxially textured buffer layer supported by the untextured barrier layer; and a biaxially textured superconducting layer supported by the biaxially textured buffer layer. Moreover, a method of forming a buffer layer on a metal substrate includes the steps of: providing a substrate having an untextured metal surface; coating the surface of the substrate with a barrier layer precursor; converting the precursor to an untextured barrier layer; and depositing a biaxially textured buffer layer above and supported by the untextured barrier layer.

The United States Government has rights in this invention pursuant to contract no. DE-AC05-00OR22725 between the United States Department of Energy and UT-Battelle, LLC.

FIELD OF THE INVENTION

The present invention relates to superconducting tapes having untextured substrates, and more particularly to chemical solution deposition of barrier layers located between the untextured substrates and textured buffer layers.

BACKGROUND OF THE INVENTION

The fabrication of YBCO coated conductors requires robust and economical production processes. A well known superconductor is YBa₂Cu₃O_(x) (YBCO), which, in order to exhibit optimum critical current density (J_(c)), is deposited on a buffered substrate, the top layer of which must be biaxially textured to provide a template for epitaxial YBCO growth. Relatively thin buffer layers are needed to optimize the engineering critical current density of YBCO conductor materials.

Well known methods of making conductor materials are ion-beam assisted deposition (IBAD) and inclined substrate deposition (ISD).

Specifically referenced and incorporated herein by reference are: U.S. Pat. No. 6,800,591 issued on Oct. 5, 2004 to Quanxi Jia, et al.; and U.S. Pat. No. 6,884,527 issued on Apr. 26, 2005 to James R. Groves, et al.

OBJECTS OF THE INVENTION

Accordingly, objects of the present invention include provision of biaxially textured templates for laminating superconductors onto untextured substrates. Further and other objects of the present invention will become apparent from the description contained herein.

SUMMARY OF THE INVENTION

In accordance with one aspect of the present invention, the foregoing and other objects are achieved by a superconducting article that includes a substrate having an untextured metal surface; an untextured barrier layer of La₂Zr₂O₇ or Gd₂Zr₂O₇ supported by and in contact with the surface of the substrate; a biaxially textured buffer layer supported by the untextured barrier layer; and a biaxially textured superconducting layer supported by the biaxially textured buffer layer.

In accordance with another aspect of the present invention, a method of forming a buffer layer on a metal substrate includes the steps of: providing a substrate having an untextured metal surface; coating the surface of the substrate with a barrier layer precursor; converting the precursor to an untextured barrier layer; and depositing a biaxially textured buffer layer above and supported by the untextured barrier layer.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a schematic sectional view of a multilayer superconductor.

For a better understanding of the present invention, together with other and further objects, advantages and capabilities thereof, reference is made to the following disclosure and appended claims in connection with the above-described drawings.

DETAILED DESCRIPTION OF THE INVENTION

The present invention relates to a scalable, non-vacuum, solution technique to deposit amorphous or nanocrystalline barrier layers on untextured Ni-alloy substrates to fabricate high performance IBAD MgO Templates. Candidate materials include but are not limited to La₂Zr₂O₇ (LZO), Gd₂Zr₂O₇ (GZO), RE₂O₃ (RE=rare earth element, atomic number 58-71), and Al₂O₃ (Alumina). Spin-coating, slot-dye coating, and dip-coating techniques used to deposit nanocrystalline and/or amorphous layers were developed at Oak Ridge National Laboratory (ORNL). Deposition of high quality (6-8° average misalignment) biaxially textured IBAD-MgO and homo-epitaxial MgO on the amorphous layer(s) was developed at Los Alamos National Laboratory (LANL). Deposition of a suitable SrTiO₃ cap and YBCO using pulsed laser deposition (PLD) was also developed at LANL. Conductors made in accordance with the present invention have achieved a J_(c) of at least 300,000 A/cm² and as high as 370,000 A/cm² at 75 K for a YBCO thickness of 1.3 μm.

One architecture for the IBAD based YBCO coated conductors utilizing CeO₂, yttria stabilized zirconia (YSZ), and MgO is YBCO/CeO₂/YSZ/IBAD-MgO/Ni-alloy. Since a very thin IBAD-deposited MgO layer is sufficient to obtain the necessary biaxial texture, it is important to provide a simplified buffer layer architecture to grow YBCO films. Thinner buffers are needed to increase the engineering critical current density of the YBCO coated conductors.

From previous demonstrations of the growth of YBCO films on LaMnO₃ (LMO)-buffered Ni substrates, we expected that the interface between LMO and YBCO should be perfect. Therefore, LMO is an alternate candidate to STO cap layer.

Buffer layer materials which have been successfully used for high-performance YBCO/IBAD-MgO films are LaMnO₃, CeO₂/LaMnO₃, SrRuO₃, and SrTiO₃. The latter buffer has resulted in reaction free interfaces with the adjacent YBCO and MgO layers and routinely achieved J_(c)s>2 MA/cm² for 1.5 μm thick YBCO films. YBCO films deposited directly on metal or buffered metal substrates delineated the need for intermediate buffering oxide films to ameliorate degradation of the superconductor caused by transition-metal elements (e.g. Ni, Cr, Mn, Mo, etc.) diffusing into it from the substrate. Thus, for improving the substrate diffusion barrier functionalities, one approach is to insert a layer below the IBAD-MgO, which would inhibit the diffusion.

FIG. 1 shows, schematically and not to scale, a multilayer superconductor comprises a substrate 1 that is generally comprised of Ni, a Ni alloy such as Hastelloy C-276, for example, Cu, a Cu alloy, or any other suitable untextured metallic composition. On the substrate is an untextured barrier layer comprising a first untextured sub-layer 2 and an optional second untextured sub-layer 3. The untextured barrier layer may comprise a single layer 2 instead of the two layers 2, 3, or it may comprise further sub-layers. The present invention is directed mainly to the untextured barrier layer.

The multilayer superconductor further comprises a biaxially textured buffer layer 4 deposited via IBAD, ISD, or other method of depositing a biaxially textured material on a non-textured substrate. Once a sufficient amount of material is deposited, a homo-epitaxial layer 5 of the same material may be deposited thereon by a less costly, conventional method such as magnetron sputter deposition, for example. The IBAD layer 4 and the homo-epitaxial layer 5 are generally integral and are generally indistinguishable in the resultant product.

An epitaxial “capping layer” 6 of STO or LMO, for example is deposited on the biaxially textured buffer layer 4 or the homo-epitaxial layer 5, or whatever the case may be. The capping layer can be deposited by any conventional method such as magnetron sputtering and pulsed laser deposition, for example. The final layer is an epitaxial superconductor layer 7 of YBCO, for example.

The multilayer superconductor may comprise additional layers or fewer layers than those described above. The total number of layers is not critical to the invention. Moreover, the compositions of the substrate and the biaxially textured layers are not critical to the invention.

The present invention involves a scalable solution approach to deposit one or more untextured (amorphous or nanocrystalline) layers (for example, 2, 3) of Al₂O₃, La₂Zr₂O₇ (LZO), Gd₂Zr₂O₇ (GZO), etc. onto the substrate 1. A layer thereof having a preferable thickness of about 50-70 nm can be deposited at ambient temperatures on the substrate. Thicknesses of the untextured layer(s) are not particularly critical to the invention, and the skilled artisan will recognize that such layer(s) can be easily adjusted to suit any particular need. Low deposition temperatures enabled by the present invention allow the untextured layer(s) to be untextured (amorphous or nanocrystalline) with the upper surface thereof replicating the smoothness of the substrate.

Films (layers) that are untextured are better diffusion barriers than larger grain polycrystalline films (e.g. buffer layers deposited at high temperatures) of equivalent thickness. The particular materials selected for the untextured layer(s) are advantageous in that, for the processing temperatures relevant to YBCO film deposition; said materials have very low diffusion coefficients for transition metals and oxygen, minimizing the thickness requirement. Moreover, electropolished Ni-alloy substrates have smooth surfaces having a Ra of <1 nm.

Chemical solution (precursor) deposition methods used to carry out the present invention can be grouped into three categories: (i) sol-gel methods that use 2-methoxyethanol as a reactant and solvent; (ii) hybrid methods that use chelating agents such as acetylacetonate or diethanolamine to reduce alkoxide reactivity, and (iii) metal-organic decomposition methods that use high-molecular-weight precursors and water-insensitive carboxylates, 2-ethyl-hexanoates. etc. The sol-gel precursor methods have been used to grow both oxide buffer layers and superconductor layers because of the ease of formation of epitaxial oxides at relatively lower temperatures, control over the polymeric viscous gel formation, and the relatively easy scale-up of the thickness of the films. In this process, metal-organic precursors are coated at room temperature and heat treated at higher temperatures and suitable atmospheres to convert the precursors to highly crystalline buffers with desired cube texture. In accordance with the present invention, it is possible to obtain untextured (e.g., amorphous and/or nanocrystalline) buffers for films processed at lower temperatures.

EXAMPLE I

Sol-gel alkoxide based LZO precursors in a concentration of 0.25-0.5 M 2-methoxyethanol solution were prepared. The precursor solutions were spin-coated with a speed of 2000 rms for 30 sec onto electropolished C276 Ni-alloy substrates. These films were converted at temperatures ranging from 500-700° C. for 30 min. XRD showed the presence of amorphous layers.

EXAMPLE II

Sol-gel alkoxide based LZO precursors in a concentration of 0.25-0.5 M 2-methoxyethanol solution were prepared. The precursor solutions were dip-coated with a line speed of 3-10 m/h onto electropolished C276 Ni-alloy substrates. These films were converted at temperatures ranging from 500-700° C. for 30 min. XRD showed the presence of amorphous layers.

EXAMPLE III

Sol-gel alkoxide based GZO precursors in a concentration of 0.25-0.5 M 2-methoxyethanol solution were prepared. The precursor solutions were spin-coated with a speed of 2000 rms for 30 sec onto electropolished C276 Ni-alloy substrates. These films were converted at temperatures ranging from 500-700° C. for 30 min. XRD showed the presence of amorphous layers.

EXAMPLE IV

Sol-gel alkoxide based GZO precursors in a concentration of 0.25-0.5 M 2-methoxyethanol solution were prepared. The precursor solutions were dip-coated with a line speed of 3-10 m/h onto electropolished C276 Ni-alloy substrates. These films were converted at temperatures ranging from 500-700° C. for 30 min. XRD showed the presence of amorphous layers.

EXAMPLE V

Sol-gel alkoxide based Y₂O₃ precursors in a concentration of 0.25-0.5 M 2-methoxyethanol solution were prepared. The precursor solutions were spin-coated with a speed of 2000 rms for 30 sec onto electropolished C276 Ni-alloy substrates. These films were converted at temperatures ranging from 500-700° C. for 30 min. XRD showed the presence of amorphous layers.

EXAMPLE VI

Sol-gel alkoxide based Y₂O₃ precursors in a concentration of 0.25-0.5 M 2-methoxyethanol solution were prepared. The precursor solutions were dip-coated with a line speed of 3-10 m/h onto electropolished C276 Ni-alloy substrates. These films were converted at temperatures ranging from 500-700° C. for 30 min. XRD showed the presence of amorphous layers.

EXAMPLE VII

Sol-gel alkoxide based Al₂O₃ precursors in a concentration of 0.25-0.5 M 2-methoxyethanol solution were prepared. The precursor solutions were spin-coated with a speed of 2000 rms for 30 sec onto electropolished C276 Ni-alloy substrates. These films were converted at temperatures ranging from 500-700° C. for 30 min. XRD showed the presence of amorphous layers.

EXAMPLE VIII

Sol-gel alkoxide based Al₂O₃ precursors in a concentration of 0.25-0.5 M 2-methoxyethanol solution were prepared. The precursor solutions were dip-coated with a line speed of 3-10 m/h onto electropolished C276 Ni-alloy substrates. These films were converted at temperatures ranging from 500-700° C. for 30 min. XRD showed the presence of amorphous layers.

EXAMPLE IX

C276 Ni-alloy substrates coated with LZO, GZO, Y₂O₃, Al₂O₃ as described in the examples above were annealed under vacuum at 500-1000° C. to study the barrier diffusion properties of these amorphous layers. Y₂O₃ is particularly useful as a second amorphous buffer (layer 3 in FIG. 1) below the IBAD-MgO layer 4.

EXAMPLE X

C276 Ni-alloy substrates coated with LZO, GZO, Y₂O₃, Al₂O₃ as described in the examples above were used as substrates for IBAD-deposited MgO layers. SrTiO₃ cap and YBCO films were subsequently deposited using pulsed laser deposition. The results are shown in Table I.

Two or more sub-layers of untextured barrier material can be deposited and converted separately or together.

The method of the present invention can be used to make conductors, semiconductors, superconductors, fault current limiters, devices, ferroelectric, photovoltaic systems, and other electrical and/or electronic devices.

While there has been shown and described what are at present considered the preferred embodiments of the invention, it will be obvious to those skilled in the art that various changes and modifications can be prepared therein without departing from the scope of the inventions defined by the appended claims. TABLE I Substrate Barrier Layer IBAD-MgO/ΔΦ YBCO/ΔΦ Jc; Thickness (LANL) (ORNL) Thickness nm (LANL) (LANL) Tc K A/cm²; μm Comments E-polished La₂Zr₂O₇ 40-50 ML204/7.8 SF1762A/4.4 85.2 370,000; 1.3 Substrate C276 Dip-coated OK E-polished Gd₂Zr₂O₇ 20-30 ML204/7.4 SF1762B/5.1 86.1  30,000; 1.4 Substrate C276 Dip-coated reacted E-polished Y₂O₃ 40-50 ML307(2)/5.6 Substrate C276 Dip-coated ML307(3)/8.5 reacted E-polished Gd₂Zr₂O₇ 20-30 ML3.0(4)/8.7 Substrate C276 Dip-coated reacted E-polished LANL standard 70 ML313(0)/4.9 Substrate C276 Ion-beam OK sputtering Al₂O₃ E-polished Y₂O₃ 40-50 ML313(1)/8.1 Substrate C276 Dip-coated 40-50 ML313(2)/8.9 reacted E-polished Gd₂Zr₂O₇ 20-30 ML313(3)/9.1 Substrate C276 Dip-coated 40-50 ML313(4)/8.9 reacted 40-50 ML313(5)/10.6 

1. A superconducting article comprising: a. a substrate having an untextured metal surface; b. an untextured barrier layer supported by and in contact with said untextured surface of said substrate, said untextured barrier layer comprising an untextured material selected from the group consisting of La₂Zr₂O₇, Gd₂Zr₂O₇, LaMnO₃, La_(0.7)Sr_(0.3)MnO₃, and YSZ; c. a biaxially textured buffer layer supported by said untextured barrier layer; and d. a biaxially textured superconducting layer supported by said biaxially textured buffer layer.
 2. A superconducting article in accordance with claim 1 wherein said substrate further comprises at least one material selected from the group consisting of Ni, Ni alloys, Cu, and Cu alloys.
 3. A superconducting article in accordance with claim 2 wherein said substrate further comprises stainless steel.
 4. A superconducting article in accordance with claim 1 wherein said biaxially textured buffer layer is in contact with said untextured barrier layer.
 5. A superconducting article in accordance with claim 1 wherein said untextured barrier layer is a first untextured barrier layer; and further comprising a second untextured barrier layer between said first untextured barrier layer and said biaxially textured buffer layer.
 6. A superconducting article in accordance with claim 5 wherein said second untextured barrier layer is in contact with said first untextured barrier layer.
 7. A superconducting article in accordance with claim 5 wherein said biaxially textured buffer layer is in contact with said second untextured barrier layer.
 8. A superconducting article in accordance with claim 5 wherein said second untextured barrier layer comprises at least one untextured material selected from the group consisting of Al₂O₃, Y₂O₃, RE₂O₃, La₂Zr₂O₇, Gd₂Zr₂O₇, and Si₃N₄.
 9. A superconducting article in accordance with claim 1 wherein said biaxially textured buffer layer further comprises at least one biaxially textured material selected from the group consisting of MgO and TiN.
 10. A superconducting article in accordance with claim 1 further comprising a biaxially textured capping layer supported by said biaxially textured buffer layer, said biaxially textured capping layer supporting said biaxially textured superconducting layer.
 11. A superconducting article in accordance with claim 10 wherein said biaxially textured capping layer is in contact with said biaxially textured buffer layer.
 12. A superconducting article in accordance with claim 10 wherein said biaxially textured superconducting layer is in contact with said biaxially textured capping layer.
 13. A superconducting article in accordance with claim 10 wherein said biaxially textured capping layer comprises at least one material selected from the group consisting of SrTiO₃, LaMnO₃, SrRuO₃, and RE₃NbO₇.
 14. A superconducting article in accordance with claim 1 wherein said biaxially textured superconducting layer comprises at least one biaxially textured material selected from the group consisting of YBCO and REBCO.
 15. A method of forming a buffer layer on a metal substrate comprising the steps of: a. providing a substrate having an untextured metal surface; b. coating said untextured surface of said substrate with a barrier layer precursor; c. converting said precursor to an untextured barrier layer; and d. depositing a biaxially textured buffer layer above and supported by said untextured barrier layer.
 16. A method in accordance with claim 15 wherein said substrate further comprises at least one material selected from the group consisting of Ni, Ni alloys, Cu, and Cu alloys.
 17. A method in accordance with claim 16 wherein said substrate further comprises stainless steel.
 18. A method in accordance with claim 15 wherein said coating step further comprises at least one technique selected from the group consisting of spin coating, slot-die coating, and dip coating.
 19. A method in accordance with claim 15 wherein converting step further comprises heating said coated substrate to a temperature in the range of 300° C. to 800° C. for a period of time not exceeding 75 minutes.
 20. A method in accordance with claim 19 wherein converting step further comprises heating said coated substrate to a temperature in the range of 400° C. to 750° C. for a period of time not exceeding 60 minutes.
 21. A method in accordance with claim 20 wherein converting step further comprises heating said coated substrate to a temperature in the range of 500° C. to 700° C. for a period of time not exceeding 45 minutes.
 22. A method in accordance with claim 15 wherein said untextured barrier layer comprises an untextured material selected from the group consisting of Al₂O₃, Y₂O₃, La₂Zr₂O₇, and Gd₂Zr₂O₇ YSZ, LaMnO₃, RE₃NbO₇, La_(0.7)Sr_(0.3)MnO₃, and RE₂O₃.
 23. A method in accordance with claim 15 wherein said untextured barrier layer is a first untextured barrier layer and wherein said method further comprises, after said converting step and before said depositing step, the additional steps of: a. coating said first untextured barrier layer with a second barrier layer precursor; and b. converting said second precursor to a second untextured barrier layer.
 24. A method in accordance with claim 23 wherein said second untextured barrier layer comprises a material selected from the group consisting of Al₂O₃, Y₂O₃, La₂Zr₂O₇, and Gd₂Zr₂O₇, YSZ, LaMnO₃, RE₃NbO₇, La_(0.7)Sr_(0.3)MnO₃, and RE₂O₃.
 25. A method in accordance with claim 15 said barrier layer precursor is a first barrier layer precursor and wherein said method further comprises, after said coating step and before said converting step, the additional step of coating said first barrier layer precursor with a second barrier layer precursor.
 26. A method in accordance with claim 15 wherein depositing step further comprises a method selected from the group consisting of ion beam assisted deposition and inclined substrate deposition.
 27. A method in accordance with claim 26 wherein said biaxially textured buffer layer further comprises at least one biaxially textured material selected from the group consisting of MgO and TiN.
 28. A method in accordance with claim 26 wherein said depositing step further comprises the additional step of homo-epitaxial deposition of additional biaxially textured buffer layer material.
 29. A method in accordance with claim 15 wherein said depositing step further comprises the additional step of depositing a biaxially textured capping layer onto said biaxially textured buffer layer.
 30. A method in accordance with claim 29 wherein said biaxially textured capping layer further comprises at least one biaxially textured material selected from the group consisting of SrTiO₃, LaMnO₃, SrRuO₃, and RE₃NbO₇.
 31. A method in accordance with claim 29 further comprising the additional step of: depositing a biaxially textured superconducting layer on said biaxially textured capping layer.
 32. A method in accordance with claim 31 wherein said biaxially textured superconducting layer further comprises at least one biaxially textured material selected from the group consisting of YBCO and REBCO. 